Catalyst mixture and polymerizable composition

ABSTRACT

A mixture of at least one thermal carbene-free ruthenium catalyst A and at least one thermal ruthenium carbene catalyst B, both of which initiate the ring-opening metathesis polymerization on their own, said catalysts being present in a weight ratio of A to B from 10:1 to 1:10. By adding this mixture even in small amounts, the ring-opening metathesis polymerization of strained cycloolefins can be effectively catalyzed.

The present invention relates to a mixture consisting of at least onethermal ruthenium catalyst A and at least one ruthenium carbene catalystB, both of which initiate the ring-opening metathesis polymerisation ontheir own, said catalysts being present in a weight ratio of A to B from10:1 to 1:10; to a composition consisting of at least one strainedcycloolefin and a catalytically effective amount of the rutheniumcatalyst mixture; to a process for the polymerisation of strainedcycloolefins; to shaped articles of polymers of said composition and tothe use of the ruthenium catalyst mixture for the ring-openingmetathesis polymerisation of strained cycloolefins.

The ring-opening metathesis polymerisation of strained cycloolefins suchas norbornene with catalysts selected from the ruthenium compound groupis known and has been repeatedly described in the literature.

A. Demonceau et al. in J. Mol. Catal. 76:123-132 (1992), for example,describe ruthenium compounds as suitable metathesis polymerisationcatalysts of e.g. norbornene, where the reactivity can be increased bythe addition of diazo esters.

In Tetrahedron Letters 52:4589-4592 (1977), C. Tanelian et al. reportthat the ruthenium compound RuCl₂ [P(C₆ H₅)₃ ]₃ is a suitable catalystfor the metathesis polymerisation but that it is deactivated bydicyclopentadiene and then no polymers are formed.

WO 93/20111 proposes the use of ruthenium compounds with phosphineligands, for example [(H₅ C₆)₃ P]₂ Cl₂ Ru═CH--CH═C(C₆ H₅)₂, as thermalcatalysts for the ring-op thesis polymerisation of strainedcycloolefins, where cyclodienes such as dicyclopentadiene act ascatalyst inhibitors and therefore cannot be polymerised. These "metalcarbenes" are sparingly soluble compounds, so that the polymerisationsare only possible in polar and, where appropriate, protic solutions. Thesame catalysts are described by S. Kanaoka in Macromolecules 1995, 28,pages 4707 to 4713 under the same conditions of solution polymerisationfor the preparation of copolymers with silicon-containing norbornenederivatives.

In Polym. Prepr. 1995, 36, pages 237 to 238, C. Fraser et al. describeruthenium carbenes having a Ru═CH--C₆ H₅ group which are effectivecatalysts for the metathesis polymerisation. A substantial disadvantageof these catalysts is their high reactivity which makes it necessary toprocess polymerisable compositions directly after the components aremixed.

WO 95/07310 describes a ring-opening photopolymerisation of strainedcycloolefins under the action of ruthenium compounds with photolabileligands as catalysts. After being irradiated, these catalysts can alsobe used as thermal catalysts.

Carbene-free ruthenium catalysts normally must be used in amounts ofmore than 0.3% by weight, and ruthenium carbene catalysts normally mustbe used in amounts of more than 0.1% by weight, based on thecycloolefin, in order to obtain, within reasonable polymerisation times,well polymerised shaped artices having good mechanical and physicalproperties. If lower amounts are used, the polymerisation is notcomplete anymore which can be detected by the inherent smell of themonomers used and their bad physical and mechanical properties. It isnot possible to prepare useful shaped articles using such low amounts.

The ruthenium catalysts are expensive and their use in higher amounts ascatalysts is uneconomical. Another disadvantage is that the use of highamounts of catalysts also leads to high amounts of ruthenium residues inthe polymers, which is undesirable for toxic reasons, adversely affectsthe stability of the polymer and must be avoided in particular wherethere is contact with electrical or electronic components.

Surprisingly, it has now been found that the high reactivity of theruthenium carbene catalysts can be reduced, a latency of polymerisablecompositions can be achieved and, within a specific scope, even thereactivity can be adjusted, which obviates immediate processing owing tothe improved storage stability achieved, if mixtures consisting ofcarbene-free (a) ruthenium catalysts and (b) ruthenium carbene catalystsare used. It has also, surprisingly, been found that despite theirlatency, the catalyst mixtures have very high reactivity and thattherefore the mixture can be used in substantially lower, andaccordingly in more economic, amounts than the individual components,still giving polymers having comparable physical and mechanicalproperties. Furthermore, the metal content in the polymers can bereduced in this manner, which enhances the properties of the polymer andwhich also permits applications in contact with electrical or electroniccomponents. The described effects are particularly pronounced whenmixtures consisting of carbene-free (a) ruthenium catalysts withphosphine ligands substituted by sterically demanding hydrocarbonradicals, and with (b) ruthenium carbene catalysts are used. It has alsobeen found that ruthenium compounds which do not initiate thepolymerisation when used in high amounts of e.g. 0.5% by weight, resultin useful shaped articles if they are added in smaller amounts inadmixture with ruthenium carbene catalysts.

In one of its aspects, this invention relates to a mixture of at leastone thermal carbene-free ruthenium catalyst A and at least one thermalruthenium carbene catalyst B, both of which initiate the ring-openingmetathesis polymerisation on their own, said catalysts being present ina weight ratio of A to B from 10:1 to 1:10.

Within the scope of this invention, thermal signifies that thering-opening metathesis polymerisation is initiated by the catalystsunder the action of heat.

The weight ratio of A to B is preferably from 8:1 to 1:2, morepreferably from 6:1 to 1:1, particularly preferably from 5:1 to 1:1 and,most preferably, from 3:1 to 1:1.

The carbene-free ruthenium catalysts A may be compounds having one(mononuclear) or two (binucluear) ruthenium atoms. The binuclearruthenium compounds may typically be the of formula XI ##STR1## whereinX₀₀₁ is Cl, Br or I, preferably Cl, and T₀₀₁ is unsubstituted or C₁ -C₆alkyl-substituted C₆ -C₁₈ arene or C₄ -C₁₇ heteroarene.

Arene preferably contains 6 to 12 carbon atoms and heteroarenepreferably contains 4 to 10 carbon atoms and 1 or 2 hetero atomsselected from the group consisting of O, N and S in one or severalrings. Arene and heteroarene can be monocyclic or condensed rings.Typical examples of alkyl substituents are methyl, ethyl, n- andi-propyl, n-, i- and t-butyl.

Typical examples of arenes are benzene, toluene, xylene, cumene,naphthalene, anthracene, naphthacene, chrysene and biphenyl. Typicalexamples of heteroarene are furan, thiophene, benzofuran,benzothiophene, pyrrole and pyridine.

Of the thermal ruthenium catalysts, those are particularly suitable andpreferred that contain phosphine ligands. Particularly preferred aredivalent-cationic ruthenium compounds containing at least one phosphinegroup and a total of 2 to 5 ligands bonded to the ruthenium atom andwhich contain acid anions for charge equalisation.

In the ruthenium compounds for use according to this invention amonophosphine can be bound to the metal atom once, twice or three times,and a diphosphine can be bound to the metal atom once. In theseruthenium catalysts a total of preferably 1 to 4, more preferably 1 to 3and, particularly preferably, 2 ligands are bonded. The phosphineligands preferably conform to formulae VII and VIIa

    PR.sub.26 R.sub.27 R.sub.28                                (VII),

    R.sub.26 R.sub.27 P--Z.sub.1 --PR.sub.26 R.sub.27          (VIIa),

wherein R₂₆, R₂₇ and R₂₈ are each independently of one another H, C₁-C₂₀ alkyl, C₁ -C₂₀ -alkoxy; C₄ -C₁₂ cycloalkyl or cycloalkoxy which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆alkoxy, or C₆ -C₁₆ aryl or C₆ -C₁₆ aryloxy which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, or C₇-C₁₆ aralkyl or C₇ -C₁₆ aralkyloxy which is unsubstituted or substitutedby C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy; R₂₆ and R₂₇ togetherare tetra- or pentamethylene or tetra- or pentamethylenedioxyl, each ofwhich is unsubstituted or substituted by C₁ -C₆ -alkyl, C₁ -C₆ haloalkylor C₁ -C₆ alkoxy, or tetra- or pentamethylene or tetra- orpentamethylenedioxyl, each of which is unsubstituted or substituted byC₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ -alkoxy and condensed with 1 or2 1,2-phenylene, or tetramethylenedioxyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy andcondensed in the 1,2- and 3,4-positions with 1,2-phenylene, and R₂₈ isas defined above; and Z₁ is linear or branched, unsubstituted or C₁ -C₄alkoxy-substituted C₂ -C₁₂ alkylene, unsubstituted or C₁ -C₄ alkyl- orC₁ -C₄ alkoxy-substituted 1,2- or 1,3-cycloalkylene of 4 to 8 carbonatoms, or unsubstituted or C₁ -C₄ alkyl- or C₁ -C₄ alkoxy-substituted1,2- or 1,3-heterocycloalkylene having 5 or 6 ring members and a heteroatom selected from the O or N group.

R₂₆, R₂₇ and R₂₈ are preferably identical. Particularly preferred arealso sterically demanding radicals, typically branched, preferablyα-branched alkyl, or cyclic radicals. Hydrocarbon radicals are alsoparticularly preferred. Preferred phoshines are those of formula VII,which are tertiary phosphines, and diphosphines of formula VIIa, whichare ditertiary diphosphines.

R₂₆, R₂₇ and R₂₈ defined as alkyl may be linear or branched and maycontain preferably 1 to 12, more preferably 1 to 8 and, particularlypreferably, 1 to 6 carbon atoms. Illustrative examples of alkyl aremethyl, ethyl, n- and i-propyl, n-, i- and t-butyl, the isomers ofpentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and eicosyl.Preferred examples are methyl, ethyl, n- and i-propyl, n-, i- andt-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.

If R₂₆, R₂₇ and R₂₈ are substituted, the substituents are preferably C₁-C₄ alkyl, C₁ -C₄ haloalkyl or C₁ -C₄ alkoxy. Halogen is preferably Cland, particularly preferably, F. Typical examples of preferredsubstituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl.R₂₆, R₂₇ and R₂₈ are preferably substituted one to three times.

R₂₆, R₂₇ and R₂₈ defined as cycloalkyl are preferably C₅ -C₈ cycloalkyland, particularly preferably, C₅ - or C₆ cycloalkyl. Some examples arecyclobutyl, cycloheptyl, cyclooctyl and, preferably, cyclopentyl andcyclohexyl. Typical examples of substituted cycloalkyl are methyl-,dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-,trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylcyclopentyland -cyclohexyl.

R₂₆, R₂₇ and R₂₈ defined as aryl are preferably C₆ -C₁₂ aryl and,particularly preferably, phenyl or naphthyl. Typical examples ofsubstituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-,dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- andtristrifluoromethylphenyl.

R₂₆, R₂₇ and R₂₈ defined as aralkyl are preferably C₇ -C₁₃ aralkyl, thealkylene group in aralkyl preferably being methylene. Aralkyl isparticularly preferably benzyl. Illustrative examples of substitutedaralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-,trimethoxy-, trifluoromethyl-, bistrifluoromethyl- andtristrifluoromethylbenzyl.

Illustrative examples of tetra- and pentamethylene which are bonded tothe P atom and which are unsubstituted or substituted or condensed, are##STR2##

Other suitable phosphines are cycloaliphates which are brigded with a═PR_(a) group containing 6 to 8 ring carbon atoms, for example ##STR3##wherein R_(a) is C₁ -C₂₀ alkyl, preferably C₁ -C₁₂ alkyl, particularlypreferably C₁ -C₆ alkyl, cyclohexyl, benzyl, or phenyl which isunsubstituted or substituted by 1 or 2 C₁ -C₄ alkyl.

Z₁ defined as linear or branched alkylene is preferably 1,2-alkylene or1,3-alkylene of preferably 2 to 6 carbon atoms, typically ethylene,1,2-propylene or 1,2-butylene.

Typical examples of Z₁ defined as cycloalkylene are 1,2- and1,3-cyclopentylene, and 1,2- or 1,3-cyclohexylene. Typical examples ofZ₁ defined as heterocycloalkylene are 1,2- and 1,3-pyrrolidine, 1,2- and1,3-piperidine, and 1,2- and 1,3-tetrahydrofuran.

In a preferred embodiment of this invention, the phosphine ligandsconform to formula VII, wherein R₂₆, R₂₇ and R₂₈ are each independentlyof one another H, C₁ -C₆ alkyl, unsubstituted or C₁ -C₄alkyl-substituted cyclopentyl or cyclohexyl, or phenyl which isunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy ortrifluoromethyl, or benzyl which is unsubstituted or substituted by C₁-C₄ alkyl, C₁ -C₄ alkoxy or trifluoromethyl. Particularly preferredexamples of phosphine ligands of formula VII are

(C₆ H₅)H₂ P, (3-CH₃ -₆ -t-C₄ H₉ --C₆ H₃)₃ P, (3-CH₃ -6-t-C₄ H₉ --C₆ H₃)₃P, PH₃, (2,6-Di-t-C₄ H₉ --C₆ H₃)₃ P, (2,3-Di-t-C₄ H₉ --C₆ H₃)₃ P,(2,4-Di-t-C₄ H₉ --C₆ H₃)₃ P, (2,4-Di-CH₃ --C₆ H₃)₃ P, (2,6-Di-CH₃ --C₆H₃)₃ P, (2-CH₃ -6-t-C₄ H₉ --C₆ H₃)₃ P, (CH₃)₃ P, (2-i-C₃ H₇ --C₆ H₄)₃ P,(3-i-C₃ H₇ --C₆ H₄)₃ P, (4-i-C₃ H₇ --C₆ H₄)₃ P, (2-n-C₄ H₉ --C₆ H₄)₃ P,(3-n-C₄ H₉ --C₆ H₄)₃ P, (4-n-C₄ H₉ --C₆ H₄)₃ P, (2-i-C₄ H₉ --C₆ H₄)₃ P,(3-i-C₄ H₉ --C₆ H₄)₃ P, (4-i-C₄ H₉ --C₆ H₄)₃ P, (2-t-C₄ H₉ --C₆ H₄)₃ P,(3-t-C₄ H₉ --C₆ H₄)₃ P, (4-t-C₄ H₉ --C₆ H₄)₃ P, (4-C₂ H₅ --C₆ H₄)₃ P,(3-n-C₃ H₇ --C₆ H₄)₃ P, (2-n-C₃ H₇ --C₆ H₄)₃ P, (4-C₃ H₇ --C₆ H₄)₃ P,(C₂ H₅)₂ HP, (3-CH₃ --C₆ H₄)₃ P, (4-CH₃ --C₆ H₄)₃ P, (2-C₂ H₅ --C₆ H₄)₃P, (3-C₂ H₅ --C₆ H₄)₃ P, (i-C₃ H₇)H₂ P, (n-C₄ H₉)H₂ P, (C₆ H₅ CH₂)₂ HP,(C₆ H₅ CH₂)H₂ P, (2-CH₃ --C₆ H₄)₃ P, (C₆ H₅)₃ P, (C₅ H₁₁)H₂ P, (C₆ H₅CH₂)₃ P, (n-C₃ H₇)₂ HP, (i-C₃ H₇)₂ HP, (n-C₄ H₉)₂ HP, (n-C₃ H₇)H₂ P, (C₂H₅)H₂ P, (C₅ H₁₁)₃ P, (C₆ H₅)₂ HP, (C₅ H₁₁)₂ HP, (n-C₃ H₇)₃ P, (i-C₃H₇)₃ P, (n-C₄ H₉)₃ P, (CH₃)₂ HP, (C₂ H₅)₃ P, (C₆ H₁₁)₃ P, (C₆ H₁₁)₂ HP,(C₅ H₉)₃ P, (C₅ H₉)₂ HP and (CH₃)H₂ P.

Particularly preferred phosphines are triphenylphosphine,tri-i-propylphosphine, tri-t-butyl-phosphine, tricyclopentylphosphineand tricyclohexylphosphine.

Ligands for the ruthenium compounds to be used according to thisinvention are organic or inorganic compounds, atoms or ions which arecoordinated to a metal centre.

Within the scope of this invention, it is particularly convenient to usethose ligands which are selected from a group of ligands (A) consistingof nitrogen (N₂); monocyclic, polycyclic or condensed arenes which areunsubstituted or substituted by OH, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₆ -C₁₂aryl or halogen and containing 6 to 24, preferably 6 to 18 and,particularly preferably, 6 to 12, carbon atoms; monocyclic heteroareneswhich are unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy orhalogen; condensed heteroarenes; condensed arene/heteroarenes containing3 to 22, preferably 4 to 16 and, particularly preferably, 4 to 10,carbon atoms, and 1 to 3 hetero atoms selected from the group consistingof 0, S and N; and aliphatic, cycloaliphatic, aromatic or araliphaticnitriles which are unsubstituted or substituted by C_(1-C) ₄ alkyl, C₁-C₄ alkoxy or halogen and containing 1 to 22, preferably 1 to 18,particularly preferably 1 to 12 and, very particularly preferably, 1 to7, carbon atoms. The preferred substituents are methyl, ethyl, methoxy,ethoxy, fluoro, chloro and bromo. The arenes and heteroarenes arepreferably substituted by one to three radicals. Of the heteroarenes theelectron-rich heteroarenes are preferred.

Some examples of arenes and heteroarenes are benzene, cumene, biphenyl,naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene,chrysene, fluoroanthrene, furan, thiophene, pyrrole, pyridine, γ-pyran,γ-thiopyran, pyrimidine, pyrazine, indole, coumarone, thionaphthene,carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole,benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline,isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine,triazines, thianthrene and purine. Preferred arenes and heteroarenes areunsubstituted or substituted benzene, naphthalene, cumene, thiophene andbenzothiophene. Arene is very particularly preferably benzene or benzenewhich is substituted by 1 to 3 C₁ -C₄ alkyl such as toluene, xylene,trimethylbenzene, isopropylbenzene, tertiary butylbenzene or cumene.Heteroarene is preferably thiophene.

The nitriles may typically be substituted by methoxy, ethoxy, fluoro orchloro. The nitriles are preferably unsubstituted. The alkyl nitrilesare preferably linear. Some examples of nitriles are acetonitrile,propionitrile, butyronitrile, pentylnitrile, hexylnitrile,cyclopentyinitrile and cyclohexylnitrile, benzonitrile,methylbenzonitrile, benzyl nitrile and naphthyl nitrile. The nitrilesare preferably linear C₁ -C₄ alkyinitriles or benzonitrile. Of thealkylnitriles, acetonitrile is particularly preferred.

In a preferred subgroup, the ligands of the group (A) are N₂, benzene,thiophene, benzonitrile or acetonitrile which are unsubstituted orsubstituted by one to three C₁ -C₄ alkyl.

Where appropriate, further ligands are present, for examples thoseselected from the ligand group (B) consisting of solvating inorganic andorganic compounds containing the hetero atoms O, S or N, which are alsooften used as solvents; and cyclopentadienyl or indenyl which areunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, (C₁ -C₄alkyl)₃ Si or (C₁ -C₄ alkyl)₃ SiO--. Typical examples of such compoundsare H₂ O, H₂ S, NH₃ ; unsubstituted or halogenated, preferablyfluorinated or chlorinated, aliphatic or cycloaliphatic alcohols ormercaptans containing 1 to 18, preferably 1 to 12 and, particularlypreferably, 1 to 6, carbon atoms, aromatic alcohols or thiols containing6 to 18, preferably 6 to 12, carbon atoms, araliphatic alcohols orthiols containing 7 to 18, preferably 7 to 12, carbon atoms; open-chainor cyclic and aliphatic, araliphatic or aromatic ethers, thioethers,sulfoxides, sulfones, ketones, aldehydes, carboxylates, lactones,carboxamides which may be N-C₁ -C₄ mono- or -dialkylated and containing2 to 20, preferably 2 to 12 and, particularly preferably, 2 to 6, carbonatoms, and lactams which may be N--C₁ -C₄ alkylated; open-chain orcyclic and aliphatic, araliphatic or aromatic, primary, secondary andtertiary amines containing 1 to 20, preferably 1 to 12 and, particularlypreferably, 1 to 6, carbon atoms; and cyclopentadienyls such ascyclopentadienyl, indenyl; cyclopentadienyls or indenyis which aremethylised or trimethylsilylated once or several times. Typical examplesalso include allyl, metallyl and crotyl.

Further examples of the ligands of group (B) are methanol, ethanol, n-and i-propanol, n-, i- and t-butanol, 1,1,1-trifluoroethanol,bistrifluoromethylmethanol, tristrifluoromethylmethanol, pentanol,hexanol, methylmercaptan or ethylmercaptan, cyclopentanol, cyclohexanol,cyclohexylmercaptan, phenol, methylphenol, fluorophenol,phenylmercaptan, benzylmercaptan, benzyl alcohol, diethyl ether,dimethyl ether, diisopropyl ether, di-n-butyl ether or di-t-butyl ether,tetrahydrofuran, tetrahydropyrane, dioxane, diethyl sulfide,tetrahydrothiophene, dimethylsulfoxide, diethylsulfoxide, tetra- andpentamethylenesulfoxide, dimethyl sulfone, diethyl sulfone, tetra- andpentamethylenesulfone, acetone, methyl ethyl ketone, diethyl ketone,phenylmethyl ketone, methylisobutyl ketone, benzylmethyl ketone,acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde,ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide,pyrrolidone and N-methylpyrrolidone, indenyl, cyclopentadienyl, methyl-or dimethyl- or pentamethylcyclopentadienyl, andtrimethylsilylcyclopentadienyl.

The primary amines may conform to formula R₂₉ NH₂, the secondary aminesto formula R₂₉ R₃₀ NH and the tertiary amines to formula R₂₉ R₃₀ R₃₁ N,wherein R₂₉ is C₁ -C₁₈ alkyl, unsubstituted or C₁ -C₄ alkyl- or C₁ -C₄alkoxy-substituted C₅ - or C₆ cycloalkyl, or unsubstituted or C₁ -C₄alkyl- or C₁ -C₄ alkoxy-substituted C₆ -C₁₈ aryl or C₇ -C₁₂ aralkyl, R₃₀independently has the meaning of R₂₉, or R₂₉ and R₃₀ together aretetramethylene, pentamethylene, 3-oxa-1,5-pentylene or -CH₂ --CH₂--NH--CH₂ --CH₂ - or -CH₂ --CH₂ --N(C₁ -C₄ alkyl)--CH₂ --CH₂ -, and R₃₁independently has the meaning of R₂₉. Alkyl preferably contains 1 to 12and, particularly preferably, 1 to 6, carbon atoms. Aryl preferablycontains 6 to 12 carbon atoms, and aralkyl preferably contains 7 to 9carbon atoms. Typical examples of amines are methyl-, dimethyl-,trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl-, dimethylethyl,n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- andbenzylamine, as well as pyrrolidine, N-methylpyrrolidine, piperidine,piperazine, morpholine and N-methylmorpholine.

In a preferred subgroup, the ligands of group (B) are H₂ O, NH₃,unsubstituted or partially or completely fluorinated C₁ -C₄ alkanols, orcyclopentadienyl, indenyl, allyi, metallyl or crotyl. H₂ O, NH₃,cyclopentadienyl, indenyl, methanol and ethanol are very particularlypreferred.

In a preferred embodiment of this invention, the Ru catalysts and Oscatalysts to be used according to this invention contain arenes orheteroarenes as ligands, phosphine groups and anions for chargeequalisation. Very particularly preferably they contain an arene groupas ligand, a tertiary phosphine group and mono- or divalent anions forcharge equalisation.

Suitable anions of inorganic or organic acids are, for example, hydride(H⁻), halide (e.g. F⁻, Cl⁻, Br⁻ and I⁻), the anion of an oxygen acid,and BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻ or AsF₆ ⁻. It may be mentioned that the aboveligands cyclopentadienyl, indenyl, allyl, metallyl and crotyl areanionic and thus also serve the charge equalisation.

Further suitable anions are C₁ -C₁₂ alcoholates, preferably C₁ -C₆alcoholates and, particularly preferably, C₁ -C₄ alcoholates, which arepreferably branched and which typically conform to formula R_(x) R_(y)R_(z) C--O⁻, wherein R_(x) is H or C₁ -C₁₀ alkyl, R_(y) is C₁ -C₁₀alkyl, and R_(y) is C₁ -C₁₀ alkyl or phenyl, the sum of the carbon atomsof R_(x), R_(y) and R_(z) being at least 2, preferably at least 3 and upto 10. Examples include in particular i-propyloxy and t-butyloxy.

Further suitable anions are C₃ -Cleacetylides, preferably C₅ -C₁₄acetylides and, particularly preferably, C₅ -C₁₂ acetylides, which mayconform to formula R_(w) --C.tbd.C⁻, wherein R_(w) is C₁ -C₁₆ -alkyl,preferably α-branched C₃ -C₁₂ alkyl, typically formula R_(x) R_(y) R_(z)C--, or phenyl or benzyl which are unsubstituted or substituted by 1 to3 C₁ -C₄ alkyl or C₁ -C₄ alkoxy. Some examples are i-propyl-, i- andt-butyl-, phenyl-, benzyl-, 2-methyl-, 2,6-dimethyl-, 2-i-propyl-,2-i-propyl-6-methyl-, 2-t-butyl-, 2,6-di-t-butyl- and2-methyl-6-t-butylphenylacetylide.

The anions of oxygen acids can be, for example, sulfate, phosphate,perchlorate, perbromate, periodate, antimonate, arsenate, nitrate,carbonate, the anion of a C₁ -C₈ -carbonic acid such as formate,acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- ortri-chloroacteate or mono-, di- or trifluoroacetate, sulfonates such asmethylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate,trifluoromethylsulfonate (triflat); phenylsulfonate or benzylsulfonatewhich is unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy orhalogen, preferably fluoro, chloro or bromo, typically tosylate,mesylate, brosyiate, p-methoxy- or p-ethoxyphenylsulfonate,pentafluorophenyisulfonate or 2,4,6-triisopropylsulfonate, andphosphonates such as methylphosphonate, ethylphosphonate,propylphosphonate, butylphosphonate, phenylphosphonate,p-methylphenylphosphonate or benzylphosphonate.

Particularly preferred are H⁻, F⁻, Cl⁻, Br⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆⁻, CF₃ SO₃ ⁻, C₆ H₅ --SO₃ ⁻, 4-methyl-C₆ H₅ --SO₃ ⁻, 3,5-dimethyl-C₆ H₅--SO₃ ⁻, 2,4,6-trimethyl-C₆ H₅ --SO₃ ⁻ and 4-CF₃ --C₆ H₅ --SO₃ ⁻ as wellas cyclopentadienyl (Cp⁻).

In a preferred embodiment of this invention, the ruthenium compoundsconform to one of formulae VIII to VIIId

    R.sub.32 L.sub.1 Me.sup.2+ (Z.sup.n-).sub.2/n              (VIII),

    R.sub.32 L.sub.1 L.sub.2 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIIa),

    (R.sub.32).sub.2 L.sub.1 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIIb),

    (R.sub.32).sub.3 L.sub.1 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIIc),

    R.sub.32 (L.sub.1).sub.2 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIId),

wherein

R₃₂ is a phosphine ligand of formula VII or VIIa;

Me is Ru;

n is 1, 2 or 3;

Z is the anion of an inorganic or organic acid;

(a) L₁ is a ligand of group A, L₁ in formula VIId being identical ordifferent, and

(b) L₂ is a ligand of group B.

R₃₂, Z, L₁ and L₂ have the meanings and preferred meanings cited abovefor the phosphines of formulae VII and VIIa.

In formulae VIII to VIIId, n is preferably 1 or 2 and, particularlypreferably, 1. R₃₂ has the preferred meanings cited for the phosphineligands of formulae VII and VIIa; they are preferably tertiaryphosphines.

It is very particularly preferred to use ruthenium compounds of one offormulae IX to IXd

    (R.sub.26 R.sub.27 R.sub.28 P)L.sub.1 Me.sup.2+ (Z.sub.1.sup.-1)Z.sub.2.sup.-1                            (IX),

    (R.sub.26 R.sub.27 R.sub.28 P).sub.2 L.sub.1 Me.sup.2+ (Z.sub.1.sup.1-)Z.sub.2.sup.-1                            (IXa),

    (R.sub.26 R.sub.27 R.sub.28 P)L.sub.1 L.sub.2 Me.sup.2+ (Z.sub.1.sup.-1)Z.sub.2.sup.-1                            (IXb),

    (R.sub.26 R.sub.27 R.sub.28 P).sub.3 L.sub.1 Me.sup.2+ (Z.sub.1.sup.-1)Z.sub.2.sup.-1                            (IXc),

    (R.sub.26 R.sub.27 R.sub.28 P)(L.sub.1).sub.2 Me.sup.2+ (Z.sub.1.sup.-1)Z.sub.2.sup.-1                            (IXd),

wherein

Me is Ru;

Z₁ and Z₂ are each independently of the other H⁻, cyclopentadienyl, Cl⁻,Br⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, CF₃ SO₃ ⁻, C₆ H₅ --SO₃ ⁻, 4-methyl-C₆H₅ --SO₃ ⁻, 3,5-dimethyl-C₆ H₅ --SO₃ ⁻, 2,4,6-trimethyl-C₆ H₅ --SO₃ ⁻ or4-CF₃ --C₆ H₅ --SO₃ ⁻ ;

R₂₆, R₂₇ and R₂₈ are each independently of one another C₁ -C₆ alkyl, orcyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy, each ofwhich is unsubstituted or substituted by 1 to 3 C₁ -C₄ alkyl, or phenylor benzyl or phenyloxy or benzyloxy, each of which is unsubstituted orsubstituted by 1 to 3 C₁ -C₄ alkyl;

L₁ is C₆ -C₁₆ arene or C₅ -C₁₆ heteroarene which is unsubstituted orsubstituted by 1 to 3 C₁ -C₄ alkyl, C₁ -C₄ alkoxy, --OH, --F or Cl, orC₁ -C₆ alkyl-CN, benzonitrile or benzylnitrile, L₁ in formula IXd beingidentical or different; and

L₂ is H₂ O or C₁ -C₆ alkanol.

If the preparation of the ruthenium catalysts is carried out in solventswhich can coordinate to a metal atom, such as to alkanols, thensolvating Ru cation complexes can form which are included within thescope of the use of the novel compositions.

Some examples of ruthenium compounds to be used according to thisinvention are: [tos signifies tosylate]: (C₆ H₁₁)₂ HPRu(p-cumene)Cl₂,(C₆ H₁₁)₃ PRu(p-cumene)Cl₂, (C₆ H₁₁)₃ PRu(p-cumene)(tos)₂, (C₆ H₁₁)₃PRu(p-cumene) Br₂, (C₆ H₁₁)₃ PRu(p-cumene)CIF, (C₆ H₁₁)₃ PRu(C₆H₆)-(tos)₂, (C₆ H₁₁)₃ PRu(CH₃ --C₆ H₅)(tos)₂, (C₆ H₁₁)₃ PRu(C₁₀H₈)(tos)₂, (i-C₃ H₇)₃ PRu(p-cumene)Cl₂, (CH₃)₃ PRu(p-cumene)Cl₂, (C₆H₁₁)₃ PRu(CH₃ --CN)(C₂ H₅ --OH)(tos)₂, (C₆ H₁₁)₃ PRu(p-cumene)-(CH₃--CN)₂ (PF₆)₂, (C₆ H₁₁)₃ PRu(p-cumene)(CH₃ --CN)₂ (tos)₂, (n-C₄ H₉)₃PRu(p-cumene)(CH₃ --CN)₂ (tos)₂, (C₆ H₁₁)₃ PRu(CH₃ CN)Cl₂, (C₆ H₁₁)₃PRu(CH₃ --CN)₂ Cl₂, (n-C₄ H₉)₃ PRu(p-cumene)Cl₂, (C₆ H₁₁)₃ PRu(p-cumene)(C₂ H₅ OH)₂ (BF₄)₂, (C₆ H₁₁)₃ PRu(p-cumene)(C₂ H₅ OH)₂ (PF₆)₂, [(C₆H₁₁)₃ P]₃ Ru(CH₃ --CN), (C₅ H₉)₃ PRu (p-cumene)Cl₂, (C₆ H₁₁)₃PRu(p-cumene)HCl, (C₆ H₁₁)₃ PRu[1,2,4,5-(CH₃)₄ C6H₂ ]Cl₂, (C₆ H₁₁)₃PRu[1,3,5-(i-C₃ H₇)₃ C₆ H₃ ]Cl₂, (C₆ H₁₁)₃ PRu-[(C₄ H₉)--C₆ H₅ ]Cl₂, (C₆H₅)₃ PRu(p-cumene)HCl, [(C₆ H₁₁)₃ P]₂ Ru(CH₃ --CN)(tos)₂, RuCl₂(p-cumene)[(C₆ H₁₁)₂ PCH₂ CH₂ P(C₆ H₁₁)₂ ], (C₆ H₁₁)₃ PRu(p-cumene)(C₂H₅ OH)(BF₄)₂, (C₆ H₁₁)₃ PRu-(C₆ H₆)(C₂ H₅ OH)₂ (tos)₂, (C₆ H₁₁)₃PRu(i-C₃ H₇ --C₆ H₅)(tos)₂, (C₆ H₁₁)₃ PRu(C₆ H₆)(p-cumene)Br₂, (C₆ H₁₁)₃PRu(biphenyl)(tos)₂, (C₆ H₁₁)₃ PRu(anthracene)(tos)₂, (2-CH₃ C₆ H₄)₃PRu(p-cumene)Cl₂ and (C₆ H₁₁)₃ PRu(chrysene)(tos)₂.

These ruthenium compounds to be used according to this invention areknown or can be prepared by known and analogous methods starting fromthe metal halides (for example RuX₃ or [RuareneX₂ ]₂ and by reactionwith phosphines and ligand formers.

The thermal ruthenium carbene catalysts B are preferably rutheniumcarbene having two phosphine ligands and two halogen atoms.

Said ruthenium carbene catalysts B may preferably conform to formula Xor Xa or to mixtures of compounds of formulae X and Xa ##STR4## whereinMe is ruthenium;

T₁ and T₂ are each independently of the other a tertiary phosphine, orT₁ and T₂ together are a ditertiary diphosphine;

T₃ is H, C₁ -C₁₂ alkyl; C₃ -C₈ cycloalkyl, C₃ -C₇ heterocycloalkylhaving one or two hetero atoms selected from the group consisting of--O--, --S-- and --N--, C₆ -C₁₄ aryl, or C₄ -C₁₅ heteroaryl having oneto three hetero atoms selected from the group consisting of --O--, --S--and --N--, which are unsubstituted or substituted by C₁ -C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁ -C₁₂ alkoxy, C₆ -C₁₀ aryl, C₆ -C₁₀ -aryloxy --NO₂ orhalogen;

T₄ is C₆ -C₁₆ arene or C₄ -C₁₅ heteroarene which is unsubstituted orsubstituted by 1 to 3 C₁ -C₄ -alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy,--OH, F, Cl or Br, and

X₀₁ and X₀₂ are each independently of the other halogen.

X₀₁ and X₀₂ in formulae X and Xa are preferably F, Cl or Br, morepreferably Cl or Br and, most preferably, each Cl.

In a preferred embodiment of this invention, T₃ is a hydrogen atom, orT₃ is a hydrocarbon radical defined within the scope of this inventioncontaining 1 to 16, more preferably 1 to 12, carbon atoms.

T₃ defined as alkyl may preferably contain 1 to 8 and, particularlypreferably, 1 to 6 carbon atoms. Some examples of alkyl are methyl,ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl and dodecyl. T₃ is particularly preferably linearC₁ -C₄ alkyl.

T₃ defined as cycloalkyl may preferably contain 5 to 8 carbon atoms.Cyclopentyl and cyclohexyl are particularly preferred.

T₃ defined as heterocycloalkyl may preferably contain 4 or 5 carbonatoms and is preferably a hetero atom selected from the group consistingof --O--, --S-- and --N--. Some examples are tetrahydrofuranyl,pyrrolidinyl, piperazinyl and tetrahydrothiophenyl. Heterocycloalkyl andaryl are preferably linked via a carbon atom of the ring.

T₃ defined as aryl may preferably contain 6 to 10 carbon atoms.Preferred examples are naphthyl and, in particular, phenyl, as well asphenyl which is substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or Cl,typically p-methylphenyl, p-ethylphenyl, p-n- or p-i-propylphenyl, p-n-,p-i- or p-t-butylphenyl, p-chlorophenyl and p-methoxyphenyl.

T₃ defined as heteroaryl may preferably contain 4 or 5 carbon atoms andone or two hetero atoms selected from the group consisting of --O--,--S-- and --N--. Some examples are furanyl, thiophenyl, pyrrolyl,pyridinyl and pyrimidinyl.

Preferred substituents for T₃ are methyl, ethyl, n- and i-propyl, n-, i-and t-butyl, methoxy, ethoxy, trichloromethyl, trifluoromethyl, phenyl,phenyloxy, F and Cl.

In a preferred embodiment of this invention, T₃ is H, C₁ -C₄ alkyl,cyclopentyl, cyclohexyl, phenyl or naphthyl, each of which isunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ -alkoxy, C₁ -C₄haloalkyl, phenyl, F or Cl.

T₄ in formula Xa defined as arene preferably contains 6 to 12 carbonatoms and, defined as heteroarene, preferably 4 to 11 carbon atoms, andpreferably contains 1 to 3 hetero atoms selected from the groupconsisting of O, S and N. Some examples of substituents for T₄ aremethyl, ethyl, n- or i-propyl, n-, i- or t-butyl, methoxy, ethoxy,trifluoromethyl, F and Cl. Preferred arenes and heteroarenes arebenzene, toluene, xylene, trimethylbenzene, naphthalene, biphenyl,anthracene, acenaphthene, fluorene, phenantrene, pyrene, chrysene,fluoroanthrene, furan, thiophene, pyrrole, pyridine, γ-pyran,y-thiopyran, pyrimidine, pyrazine, indole, coumarone, thionaphthene,carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole,benzimidazole, oxazole, thiazole, isooxazole, isothiazole, quinoline,isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine,triazine, thianthrene, and purine. Particularly preferred arenes andheteroarenes are benzene, naphthalene, cumene, thiophene andbenzthiophene. Arene is very particularly preferably benzene or benzenesubstituted by C₁ -C₄ alkyl, such as toluene, xylene, isopropylbenzene,tertiary butylbenzene or cumene; and heteroarene is particularlypreferably thiophene.

The phosphine group T₁ and T₂ is preferably tertiary phosphines orditertiary diphosphines containing 3 to 40, more preferably 3 to 30 and,particularly preferably, 3 to 24, carbon atoms.

The tertiary phosphine and ditertiary diphosphine groups have themeanings and preferred meanings stated above for formulae VII and VIIa.

A preferred subgroup of the compounds of formulae X and Xa are those offormulae Xb and Xc ##STR5## wherein Me is Ru, R₂₉ is α-branched C₃ -C₈alkyl, C₅ -C₈ cycloalkyl which is unsubstituted or substituted by C₁ -C₄alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, halogen or --NO₂, or C₆ -C₁₀aryl which is unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, halogen or --NO₂, T₃ is H, C₁ -C₆ alkyl, C₅-C₈ cycloalkyl which is unsubstituted or substituted by C₁ -C₄ alkyl, C₁-C₄ haloalkyl, C₁ -C₄ alkoxy, halogen or --NO₂, or C₆ -C₁₀ aryl which isunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄alkoxy, halogen or --NO₂, and T₄ is phenyl or phenyl substituted by 1 to3 C₁ -C₄ alkyl.

Some specific and preferred examples are [Me signifies Ru(IV)]: Cl₂[P(C₆ H₁₁)₃ ]₂ Me═CH--C₆ H₅, Cl₂ [P(C₅ H₉)₃ ]₂ Me═CH--C₆ H₅, Br₂ [P(C₆H₁₁)₃ ]₂ Me═CH--C₆ H₅, Br₂ --[P(C₅ H₉)₃ ]₂ Me═CH--C₆ H₅, F₂ [P(C₆ H₁₁)₃]₂ Me═CH--C₆ H₅, F₂ [P(C₅ H₉)₃ ]₂ Me═CH--C₆ H₅, Cl₂ [P(C₆ --H₁₁)₃ ]₂Me═CH (C₆ H₄ --Cl), Cl₂ [P(C₅ H₉)₃ ]₂ Me═CH(C₆ H₄ --Br), Br₂ [P(C₆ H₁₁)₃]₂ Me═CH(C₆ H₄ --NO₂), Br₂ [P(C₅ H₉)₃ ]₂ Me═CH(C₆ H₄ --OC₂ H₅)₂, Cl₂[P(C₆ H₁₁)₃ ]₂ Me═CH(C₆ H₄ --CH₃), F₂ [P(C₅ H₉)₃ ]₂ Me═CH--[C₆ H₃--(CH₃)₂ ], Cl₂ [P(C₆ H₁₁)₃ ]₂ Me═CH--C₁₀ H₉, Cl₂ [P(C₅ H₉, Cl₂ [P(C₅H₉)₃ ]₂ Me═CH--CH₃, Cl₂ [P(C₆ H₁₁)₃ ]₂ Me═CHCH₃, Br₂ [P(C₅ H₉)₃ ]₂Me═CH-i-C₃ H₇, Cl₂ [P(C₆ H₁₁)₃ ]₂ Me═CH-t-C₄ H₉, Cl₂ [P(C₅ H₉)₃ ]₂Me═CH-n-C₄ H₉, Cl₂ [P(C₆ H₁₁)₃ ]₂ Me═CH--C₆ H₄ --OCH₃, Cl₂ [P(C₅ H₉)₃ ]₂Me═CH--C₆ H₃ --(CH₃)₂, Br₂ [P(C₆ --H₁₁)₃ ]₂ Me═CH--C₆ H₂ --(CH₃)₃, Br₂[P(C₅ H₉)₃ ]₂ Me═CH--CH₂ C₆ H₅, Cl₂ [P(t-C₄ H₉)₃ ]₂ Me═CH--C₆ H₅, Cl₂--[P(i-C₃ H₇)₃ ]₂ Me═CH--C₆ H₅, Cl₂ [P(C₆ H₅)₃ ]₂ Me═CH--C₆ H₅, Cl₂[P(C₆ H₃ --CH₃)₃ ]₂ Me═CH--C₆ H₅, Br₂ --[P(C₅ H₄ --(CH₃)₂ ]₃ ]₂Me═CH--C₆ H₅, Cl₂ [P(C₆ H₃ --(CH₃)₃ ]₂ Me═CH--C₆ H₅, Cl₂ [P(C₆ H₁₁)₃--CH₂ CH₂ --P(C₆ H₁₁)₃ ]Me═CH--C₆ H₅, Cl₂ [P(C₅ H₉)₃ ]₂ Me═CH--C₆ H₁₁,Cl₂ [P(C₅ H₉)₃ ]₂ Me═CH--C₅ H₉, Cl₂ [P(C₅ --H₉)₃ ]₂ Me═C(C₆ H₁₁)₂, Cl₂[P(C₆ H₁₁)₃ ]₂ Me═CH₂, Cl₂ [P(C₅ H₉)₃ ]₂ Me═CH₂, Cl₂ [P(C₆ H₁₁)₃ ]₂Me═CH-n-butyl, Cl₂ [P(i-C₃ H₇)₃ ]₂ Me═CH--C₆ H₅, Cl₂ [P(i-C₃ H₇)₃ ]₂Me═CH--C₅ H₁₁.

The compounds of formula X are known and their preparation is describedby P. Schwab et al. in Angew. Chem. (1995), 107, No. 18, pages 2179 to2181. The binocular compounds of formula Xa can be prepared, forexample, by reacting 2 equivalents of a compound of formula X with oneequivalent of a per se known compound of formula ##STR6## wherein X₀₂,Me and T₄ have the meanings stated for formula Xa, in the presence of aninert solvent.

Particularly preferred novel mixtures are those, wherein the rutheniumcatalyst A conforms to formula IXe,

    (R.sub.26 R.sub.27 R.sub.28 P)L.sub.1 Ru.sup.2+ (Z.sub.1.sup.-1).sub.2(IXe),

wherein R₂₆, R₂₇ and R₂₈ have the meanings stated above, including thepreferred meanings, L₁ is an arene or heteroarene, including thepreferred meanings stated above, and Z₁ ¹⁻ is Cl⁻, Br⁻, BF₄ ⁻, PF₆ ⁻,SbF₆ ⁻, AsF₆ ⁻, CF₃ SO₃ ⁻, C₆ H₅ --SO₃ ⁻, 4-methyl-C₆ H₅ --SO₃ ⁻,3,5-dimethyl-C₆ H₅ --SO₃ ⁻, 2,4,6-trimethyl-C₆ H₅ --SO₃ ⁻ or 4-CF₃ --C₆H₅ --SO₃ ⁻ ; and the ruthenium carbene catalyst B conforms to formula Xand, particularly preferably, to formula Xb.

The novel mixtures are excellently suitable as catalysts for thering-opening metathesis polymerisation of strained cycloolefins.

In another of its aspects, the invention relates to a compositionconsisting of (a) at least one strained cycloolefin and (b) acatalytically effective amount of a mixture of at least one thermalcarbene-free ruthenium catalyst A and at least one thermal rutheniumcarbene catalyst B, both of which initiate the ring-opening metathesispolymerisation on their own, said catalysts being present in a weightratio of A to B from 10:1 to 1:10. The catalysts in the novelcompositions have the same preferred meanings as described above.

Catalytically effective signifies that the mixture is used in amountswhich give, at a defined polymerisation cycle for a specific cycloolefin(see Examples), shaped articles having better physical and mechanicalproperties than when half the amount is used as individual components.

In a preferred embodiment of this invention, the amount of the novelmixture in the composition is from 0.05 to 0.3% by weight, preferablyfrom 0.05 to 0.25% by weight and, most preferably, from 0.1 to 0.2% byweight, based on the amount of the cycloolefins present.

The cyclic olefins may be monocyclic or polycyclic condensed and/orbridged and/or linked ring systems, for example having from two to fourrings, which are unsubstituted or substituted and may contain heteroatoms, for example an O, S, N or Si atom, in one or more than one ringand/or may contain condensed aromatic or heteroaromatic rings, forexample o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene.The individual cyclic rings may contain from 3 to 16, preferably from 3to 12 and, particularly preferably, from 3 to 8, ring members. Thecyclic olefins may contain further non-aromatic double bonds,preferably, depending on the ring size, from 2 to 4 such additionaldouble bonds. The ring substituents are inert, that is to say they donot adversely affect the chemical stability and the thermal stability ofthe ruthenium and osmium catalysts. The cycloolefins are strained ringsor ring systems. Individual rings and ring systems having from 5 to 8carbon atoms in the ring are particularly preferred.

When the cyclic olefins contain more than one double bond, for examplefrom 2 to 4 double bonds, or when mixtures of strained cycloolefinshaving one double bond and strained cycloolefins having at least twodouble bonds, for example from 2 to 4 double bonds, are used, then,depending on the reaction conditions, the monomer chosen and the amountof catalyst, it is also possible for crosslinked polymers to be formed.

In a preferred embodiment of the composition according to the invention,the cycloolefins conform to formula II ##STR7## wherein Q₁ is a radicalhaving at least one carbon atom which, together with the --CH═CQ₂ --group, forms an at least 3-membered alicyclic ring which may contain oneor more than one hetero atom selected from the group consisting of Si,P, O, N and S; and which is unsubstituted or substituted by halogen, ═O,--CN, --NO₂, R₁ R₂ R₃ Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M,--COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀ alkyl, C₁-C₂₀ hydroxyalkyl, C₁ -C₂₀ haloalkyl, C₁ -C₆ cyanoalkyl, C₃ -C₈cycloalkyl, C₆ -C₁₆ aryl, C₇ -C₁₆ aralkyl, C₃ -C₆ -heterocycloalkyl, C₃-C₁₆ heteroaryl, C₄ -C₁₆ heteroaralkyl or by R₄ --X--; or wherein twoadjacent carbon atoms, when present, are substituted by --CO--O--CO-- orby --CO--NR₅ --CO--; or wherein an alicyclic, aromatic or heteroaromaticring has been fused to adjacent carbon atoms of the alicyclic ring, theformer ring being unsubstituted or substituted by halogen, --CN, --NO₂,R₆ R₇ R₈ Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2),--SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀ alkyl, C₁ -C₂₀ hydroxyalkyl,C₁ -C₆ cyanoalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇ -C₁₆ aralkyl, C₃-C₆ heterocycloalk, C₃ -C₁₆ heteroaryl, C₄ -C₁₆ heteroaralkyl or by R₁₃--X₁ --; X and X₁ are each independently of the other --O--, --S--,--CO--, --SO--, --SO₂ --, --O--C(O)--, --C(O)--O--, --C(O)--NR₅ --,--NR₁₀ --C(O)--, --SO₂ --O-- or --O--SO₂ --; R₁, R₂ and R₃ are eachindependently of one another C₁ -C₁₂ alkyl, C₁ -C₁₂ perfluoroalkyl,phenyl or benzyl; R₄ and R₁₃ are each independently of the other C₁ -C₂₀alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆-C₁₆ aryl or C₇ -C₁₆ -aralkyl; R₅ and R₁₀ are each independently of theother hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl, the alkyl groups inturn being unsubstituted or substituted by C₁ -C₁₂ alkoxy or by C₃ -C₈cycloalkyl; R₆, R₇ and R₈ are each independently of one another C₁ -C₁₂alkyl, C₁ -C₁₂ perfluoroalkyl, phenyl or benzyl; M is an alkali metaland M₁ is an alkaline earth metal; and u is 0 or 1; it being possiblefor the alicyclic ring formed with Q₁ to contain further non-aromaticdouble bonds;

Q₂ is hydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₁₂ alkoxy,halogen, --CN or R₁₁ --X₂ --, wherein R₁₁ is C₁ -C₂₀ alkyl, C₁ -C₂₀haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl or C₇-C₁₆ aralkyl, and X₂ is --C(O)--O-- or --C(O)--NR₁₂ --, wherein R₁₂ ishydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

the above-mentioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl,aralkyl and heteroaralkyl groups being unsubstituted or substituted byC₁ -C₁₂ alkyl, C₁ -C₁₂ alkoxy, --NO₂, --CN or by halogen, and the heteroatoms of the above-mentioned heterocycloalkyl, heteroaryl andheteroaralkyl groups being selected from the group consisting of --O--,--S--, --NR₉ -- and --N═; and R₉ is hydrogen, C₁ -C₁₂ alkyl, phenyl orbenzyl.

Fused alicyclic rings contain preferably from 3 to 8, more preferablyfrom 5 to 8 and, most preferably, 5 or 6, ring carbon atoms.

When an asymmetric centre is present in the compounds of formula I, thecompounds may occur in optically isomeric forms. Some compounds offormula I may occur in tautomeric forms (for example keto-enoltautomerism). When an aliphatic C═C double bond is present, geometricisomerism (E-form or Z-form) may also occur. Exo-endo configurations arealso possible. Formula I therefore includes all possible stereoisomerspresent in the form of enantiomers, tautomers, diastereoisomers,E/Z-isomers or mixtures thereof.

In the definitions of the substituents, the alkyl, alkenyl and alkynylgroups may be straight-chain or branched. The same applies also to the(or each) alkyl moiety of alkoxy, alkylthio and alkoxycarbonyl and otheralkyl-containing groups. These alkyl groups contain preferably from 1 to12, more preferably from 1 to 8 and, most preferably, from 1 to 4,carbon atoms. These alkenyl and alkynyl groups contain preferably from 2to 12, more preferably from 2 to 8 and, most preferably, from 2 to 4,carbon atoms.

Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl,n-butyl, isobutyl, tert-butyl and the various isomeric pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosylradicals.

Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl,1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl,1-hydroxyisobutyl, 1-hydroxy-sec-butyl, 1-hydroxytert-butyl and thevarious isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl and eicosyl radicals.

Haloalkyl includes, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyland also halogenated, preferably fluorinated or chlorinated, alkanes,for example isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl,tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Alkenyl includes, for example, propenyl, isopropenyt, 2-butenyl,3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl,n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl andn-octadec-4-enyl.

Cycloalkyl is preferably C₅ -C₈ cycloalkyl, in particular C₅ - or C₆cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropyl,cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl andcyclooctyl.

Cyanoalkyl includes, for example, cyanomethyl (methylnitrile),cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl,2-cyano-n-butyl, 1-cyano-isobutyl, 1-cyano-sec-butyl, 1-cyano-tert-butyland the various isomeric cyanopentyl and cyanohexyl radicals.

Aralkyl contains preferably from 7 to 12 carbon atoms and, morepreferably, from 7 to 10 carbon atoms. It may be, for example, benzyl,phenethyl, 3-phenylpropyl, α-methylbenzyl, phenbutyl orα,α-dimethylbenzyl.

Aryl preferably contains from 6 to 10 carbon atoms. It may be, forexample, phenyl, pentaline, indene, naphthalene, azulene or anthracene.

Heteroaryl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the group O, S and N. It may be, for example, pyrrole, furan,thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine,pyridazine, indole, purine or quinoline.

Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or twohetero atoms from the group O, S and N. It may be, for example, oxirane,azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine,piperazine, morpholine, tetrahydrofuran or tetrahydrothiophene.

Alkoxy is, for example, methoxy, ethoxy, propyloxy, isopropyloxy,n-butyloxy, isobutyloxy and tert-butyloxy.

Within the scope of this invention, an alkali metal is to be understoodas being lithium, sodium, potassium, rubidium or caesium, preferablylithium, sodium or potassium.

Within the scope of this invention, an alkaline earth metal will beunderstood as being beryllium, magnesium, calcium, strontium or barium,preferably magnesium or calcium.

In the above definitions, halogen will be understood as being fluoro,chloro, bromo or iodo, preferably fluoro, chloro or bromo.

Compounds of formula II that are particularly suitable for thecomposition according to the invention are those wherein Q₂ is hydrogen.

Also preferred for the composition are compounds of formula II in whichthe alicyclic ring formed by Q₁ together with the --CH═CQ₂ -- group hasfrom 3 to 16, preferably from 3 to 12, more preferably from 3 to 8, and,most preferably, from 5 to 8, ring atoms, and which may be monocyclic,bicyclic, tricyclic or tetracyclic ring systems.

It is especially advantageous when the composition according to theinvention comprises compounds of formula II, wherein

Q₁ is a radical having at least one carbon atom which, together with the--CH═CQ₂ -- group, forms a 3- to 20-membered alicyclic ring which maycontain one or more than one hetero atom selected from the group Si, O,N and S; and which is unsubstituted or substituted by halogen, ═O, --CN,--NO₂, R₁ R₂ R₃ Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M,--COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁ -C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇-C₁₂ aralkyl, C₃ -C₆ heterocycloalkyl C₃ -C₁₂ heteroaryl, C₄ -C₁₂heteroaralkyl or by R₄ --X--; or wherein two adjacent carbon atoms inthat radical Q₁ are substituted by --CO--O--CO-- or by --CO--NR₅ --CO--;or wherein an alicyclic, aromatic or heteroaromatic ring may have beenfused to adjacent carbon atoms, which ring is unsubstituted orsubstituted by halogen, --CN, --NO₂, R₆ R₇ R₈ Si--, --COOM, --SO₃ M,--PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₁₂alkyl, C₁ -C₁₂ -haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₁ -C₄ cyanoalkyl, C₃-C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇ -C₁₂ aryl, C₇ -C₁₂ -aralkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₁₂ heteroaralkyl or by R₁₃--X₁ --; X and X₁ are each independently of the other --O--, --S--,--CO--, --SO--, --SO₂ --, --O--C(O)--, --C(O)--O--, --C(O)--NR₅ --,--NR₁₀ --C(O)--, --SO₂ --O-- or --O--SO₂ --; and R₁, R₂ and R₃ are eachindependently of one another C₁ -C₆ alkyl, C₁ -C₆ perfluoroalkyl, phenylor benzyl; M is an alkali metal and M₁ is an alkaline earth metal; R₄and R₁₃ are each independently of the other C₁ -C₁₂ alkyl, C₁ -C₁₂haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₂ aryl or ₇-C₁₂ aralkyl; R₅ and R₁₀ are each independently of the other hydrogen,C₁ -C₆ alkyl, phenyl or benzyl, the alkyl groups in turn beingunsubstituted or substituted by C₁ -C₆ -alkoxy or by C₃ -C₆ cycloalkyl;R₆, R₇ and R₈ are each independently of the other C₁ -C₆ alkyl, C₁ -C₆perfluoroalkyl, phenyl or benzyl; u is 0 or 1; it being possible for thealicyclic ring formed with Q₁ to contain further non-aromatic doublebonds;

Q₂ is hydrogen, C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₆ alkoxy,halogen, --CN or R₁₁ --X₂ --, wherein R₁₁, is C₁ -C₁₂ alkyl, C₁ -C₁₂haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl or C₇-C₁₂ aralkyl, and X₂ is --C(O)--O-- or --C(O)--NR₁₂ --, wherein R₁₂ ishydrogen, C₁ -C₆ alkyl, phenyl or benzyl;

and the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl andheteroaralkyl groups being unsubstituted or substituted by C₁ -C₆ alkyl,C₁ -C₆ alkoxy, --NO₂, --CN or by halogen, and the hetero atoms of theheterocycloalkyl, heteroaryl and heteroaralkyl groups being selectedfrom the group consisting of --O--, --S--, --NR₉ -- and --N═; and R₉ ishydrogen, C₁ -C₆ alkyl, phenyl or benzyl.

From that group preference is given to those compounds of formula oil,wherein

Q₁ is a radical having at least one carbon atom which, together with the--CH═CQ₂ -- group, forms a 3- to 10-membered alicyclic ring which maycontain a hetero atom selected from the group Si, O, N and S, and whichis unsubstituted or substituted by halogen, --CN, --NO₂, R₁ R₂ R₃ Si--,--COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ hydroxyalkyl, C₁ -C₄cyanoalkyl, C₃ -C₆ cycloalkyl, phenyl, benzyl or by R₄ --X--; or whereinan alicyclic, aromatic or heteroaromatic ring may have been fused toadjacent carbon atoms, which ring is unsubstituted or substituted byhalogen, --CN, --NO₂, R₆ R₇ R₈ Si--, --COOM, --SO₃ M, --PO₃ M,--(COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₆ alkyl, C₁-C₆ haloalkyl, C₁ -C₆ hydroxyalkyl, C₁ -C₄ cyanoalkyl, C₃ -C₆cycloalkyl, phenyl, benzyl or by R₁₃ --X₁ --; R₁, R₂ and R₃ are eachindependently of one another C₁ -C₄ alkyl, C₁ -C₄ perfluoroalkyl, phenylor benzyl; M is an alkali metal and M₁ is an alkaline earth metal; R₄and R₁₃ are each independently of the other C₁ -C₆ alkyl, C₁ -C₆haloalkyl, C₁ -C₆ hydroxyalkyl or C₃ -C₆ cycloalkyl; X and X₁ are eachindependently of the other --O--, --S--, --CO--, --SO-- or --SO₂ --; R₆,R₇ and R₈ are each independently of one another C₁ -C₄ alkyl, C₁ -C₄perfluoroalkyl, phenyl or benzyl; and

Q₂ is hydrogen.

The composition according to the invention preferably comprisesnorbornene and norbornene derivatives, norbornadiene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene or cyclododecene. Of thenorbornene derivatives, special preference is given to thosecorresponding to formula III ##STR8## wherein X₃ is --CHR16--, oxygen orsulfur;

R₁₄ and R₁₅ are each independently of the other hydrogen, --CN,trifluoromethyl, (CH₃)₃ Si--O--, (CH₃)₃ Si-- or --COOR₁₇ ; and

R₁₆ and R₁₇ are each independently of the other hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl; or to formula IV ##STR9## wherein X₄ is --CHR₁₉ --,oxygen or sulfur;

R₁₈ is hydrogen, C₁ -C₆ alkyl or halogen; and

R₁₉ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

or to formula V ##STR10## wherein X₅ is --CHR₂₂ --, oxygen or sulfur;

R₂₀ and R₂₁ are each independently of the other hydrogen, CN,trifluoromethyl, (CH₃)₃ Si--O--,

(CH₃)₃ Si-- or --COOR₂₃ ; and

R₂₂ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

R₂₃ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

or to formula VI, ##STR11## wherein X₆ is --CHR₂₄ --, oxygen or sulfur;

Y is oxygen or >N--R₂₅,

R₂₄ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl; and

R₂₅ is hydrogen, methyl, ethyl or phenyl.

Another preferred subgroup of monomers is formed by those composed onlyof carbon and hydrogen.

The following compounds of formula I which may be preparable byDiels-Alder reactions are some specific examples, it being possible forthe oxanorbornene derivatives also to be norbornene derivatives and viceversa: ##STR12## R₀ can, for example, be an epoxy, acrylate ormethacrylate group which is covalently bonded to the cyclooctenedirectly or via a bridge group.

Condensed and/or bridged and/or linked olefinically unsaturated ringsystems are generally prepared by means of Diels-Alder reactions. Theyshould be fusable without decomposition which, within the scope of theinvention, means that strained cycloolefins can be fused and thecatalyst can be dissolved. In the case of thermally labile strainedcycloolefins it may therefore be necessary to dissolve the catalystunder pressure. Where the reaction temperature is higher than thedecomposition temperature of the strained cycloolefin, it is advisableto carry out the procedures under pressure in order to avoiddecomposition of the monomers prior to polymerisation.

A preferred subgroup are the Diels-Alder adducts of cyclopentadienes,many of which are known and are commercially available (they areobtained, for example, in petroleum distillation), or which can beprepared in known manner by a Diels-Alder reaction of cyclopentadieneswith cyclopentadienes, or with Diels-Alder adducts of cyclopentadienes(oligocyclopentadienes). These Diels-Alder adducts can conform toformula I ##STR13## wherein p is 0 or a number from 1 to 100, preferablyfrom 1 to 50, particularly preferably from 1 to 20 and, most preferably,from 1 to 10, and wherein the adduct may be substituted as stated abovefor the Diels-Alder adducts, preferably by C₁ -C₆ alkyl groups.

Illustrative examples of compounds of formula I are ##STR14## as well astricyclopentadiene.

Another preferred subgroup of Diels-Alder adducts are those ofunsubstituted or substituted norbornenes or norbornadienes withunsubstituted or substituted 1,3-cyclopentadienes. Particularlypreferred Diels-Alder adducts are those of formula Ia ##STR15## whereinq is preferably a number from 1 to 20, more preferably from 1 to 10 and,particularly preferably, from 1 to 5, the Diels-Alder adducts beingunsubstituted or substituted by, preferably, C₁ -C₆ alkyl.

Illustrative examples of compounds of formula Ia are ##STR16##

The composition according to the invention may additionally containfurther open-chain comonomers that form copolymers with the strainedcycloolefins. When dienes are additionally used, for example,crosslinked polymers may be formed. Some examples of such comonomers areolefinically mono- or di-unsaturated compounds, such as olefins anddienes from the group ethene, propene, butene, pentene, hexene, heptene,octene, decene, dodecylene, cyclohexene (which, as is known, does notform metathesis polymers on its own), acrylic and methacrylic acid andthe esters and amides thereof, vinyl ethers, vinyl esters, vinylchloride, vinylidene chloride, styrene, butadiene, isoprene andchlorobutadiene. When volatile comonomers are additionally used, it isoften necessary to carry out the procedures under pressure. Theadditional use of non-volatile comonomers can therefore be of advantageto the method.

The further open-chain olefins suitable for copolymerisation are presentin the novel composition in an amount of typically up to 80% by weight,preferably from 0.1 to 80% by weight, more preferably from 0.5 to 60% byweight and, most preferably, from 5 to 40% by weight, based on the totalamount of compounds of di- and oligocyclopentadienes and further olefinscapable of copolymerisation.

The composition according to the invention may contain formulationauxiliaries. Known auxiliaries are antistatics, antioxidants, lightstabilisers, plasticisers, dyes, pigments, fillers, reinforcing fillers,lubricants, adhesion promoters, viscosity-increasing agents anddemoulding auxiliaries. The fillers may be present in surprisingly highproportions without having an adverse effect on the polymerisation, forexample in amounts of up to 80% by weight, preferably from 1 to 70% byweight, more preferably from 5 to 70% by weight, particularly preferablyfrom 5 to 60% by weight and, most preferably, from 10 to 60% by weight,based on the composition. A great variety of fillers and reinforcingfillers for improving the optical, physical, mechanical and electricalproperties is known. Some examples are glass and quartz in the form ofpowders, beads and fibres, metal and semi-metal oxides, carbonates suchas MgCO₃, CaCO₃, dolomite, metal sulfates such as gypsum and barite,natural and synthetic silicates such as talc, zeolites, wollastonite,feldspars, argillaceous earths, such as China clay, crushed stone,whiskers, carbon fibres, plastics fibres or powders, and carbon black.Viscosity-increasing agents are in particular metathesis polymers thathave olefinically unsaturated groups and can be incorporated into thepolymer during polymerisation. Such metathesis polymers are known andare commercially available, for example, under the trade nameVestenamere®. For the same purpose it is also possible to use, forexample, poly-1,3-dienes such as polybutadiene, polyisoprene,polychlorobutadiene or copolymers with the basic dienes and one or moreolefins. Such polymers are also commercially available, for exampleBuna® and Kraton®. The amount of viscosity-increasing polymers can be,for example, from 0.1 to 50% by weight, preferably from 1 to 30% byweight and, preferably, from 1 to 20% by weight, based on all themonomers present in the composition. The viscosity-increasing agentsserve simultaneously to improve the viscous properties of the polymers.The viscosity of the composition can be adjusted to the desiredapplications within a wide scope.

The compositions according to the invention are excellently suitable forthe direct preparation of shaped articles. Although the catalystactivity is in some cases high, the individual components can be mixedand brought into the desired form because the catalysts dissolve innon-polar and polar monomers even at room temperature or with slightheating. Solubilisers (solvents such as methylene chloride,tetrahydrofuran) can be additionally used and are conveniently removedagain before polymerisation. Besides direct preparation of shapedarticles, it is also possible to carry out polymerisations in solutionor emulsions, the polymers only then being further processed to shapedarticles.

In another of its aspects, this invention relates to a process for thepreparation of polymers by metathesis polymerisation, which comprisesheating a novel composition.

The preferred meanings of the novel process are the same as those of thenovel compositions.

The compositions according to the invention are relativelystorage-stable, but monomers and catalyst are expediently mixed togetheronly just before processing. The process according to the invention isadvantageously carried out in such a manner that shaping, for example togive a coating or a moulding, is combined with the mixing and takesplace prior to the polymerisation. In principle, all known shapingprocedures, for example extrusion, injection moulding and compressionprocedures, can be used. The compositions according to the invention aresuitable especially as casting resins where appropriate with theapplication of pressure, for example as in RIM processes (ReactionInjection Moulding).

"Heating" may represent a temperature from 30 to 300° C., preferablyfrom 40 to 300° C., more preferably from 50 to 250° C., particularlypreferably from 60 to 250° C. and, most preferably, from 60 to 200° C.The polymerisation times depend essentially on the catalyst activity andthe times can vary from seconds to minutes up to several hours. Thepolymerisation can also be carried out stepwise with increasingtemperatures.

Using the process according to the invention it is possible to producematerials (semi-finished articles) for the preparation of mouldings bymeans of machining techniques or to prepare directly all kinds ofmouldings, films, foils and coatings. The invention relates also to theuse of the novel composition for the preparation of semi-finishedarticles, mouldings and foils. The invention relates also to mouldingsmade from the compositions according to the invention.

Depending on the monomer used, the polymers according to the inventionmay have very different properties. Some are distinguished by a veryhigh degree of oxygen permeability, low dielectric constants, goodthermal stability and low water absorption. Others have excellentoptical properties, for example high transparency and low refractiveindices. Special mention should also be made of the low degree ofshrinkage. They can therefore be used in a very wide variety oftechnical fields. The avoidance of solvents ensures the production ofbubble-free mouldings and coatings even at relatively highpolymerisation temperatures.

When used as coatings on the surfaces of support materials, inparticular non-polar support materials, the novel compositions aredistinguished by high adhesive strength. A physical treatment (forexample plasma treatment) or chemical treatment (application of adhesionpromoters) can further improve the adhesive strength. The coatedmaterials are also distinguished by a very high degree of surfacesmoothness and gloss. Among their good mechanical properties, specialmention should be made of the low degree of shrinkage and the highimpact strength, and also the thermal stability. In addition, they canbe readily demoulded when processed in moulds and have a high resistanceto solvents. The properties desired in final use can be adjustedselectively by way of the monomers chosen. In addition to rigid andresilient thermoplastic mouldings it is also possible to obtaincrosslinked thermosetting or elastomeric polymers.

These polymers are suitable for the production of medical apparatus,implants or contact lenses; for the production of electronic components;as binders for surface-coatings; as photocurable compositions formodel-making or as adhesives for bonding substrates having low surfaceenergies (for example Teflon, polyethylene and polypropylene).

The compositions according to the invention are particularly suitablefor the preparation of protective coatings on substrates or supportmaterials. The invention relates also to a variant of the processaccording to the invention for the preparation of coatings on supportmaterials in which a composition according to the invention is appliedas a coating to a support, for example by means of immersion, spreading,pouring, rolling, knife-application or centrifugal moulding procedures,and the coating is heated for the purpose of polymerisation. This may befollowed by heat treatment. Surfaces of substrates can be modified orprotected using that method.

This invention relates also to a composition consisting of (a) a supportmaterial and (b) a coating of a composition according to the inventionwhich is applied to at least one surface.

This invention relates likewise to a composition consisting of (a) asupport material and (b) a polymeric coating of a composition accordingto the invention which is applied to at least one surface.

Suitable substrates (support materials) are, for example, glass,minerals, ceramics, plastics, wood, semi-metals, metals, metal oxidesand metal nitrides. The coating thicknesses depend essentially on thedesired use and may be, for example, from 0.1 to 1000 μm, preferablyfrom 0.5 to 500 μm, more preferably from 1 to 100 μm. The coatedmaterials are distinguished by high adhesive strength and good thermaland mechanical properties.

The preparation of the coated materials according to the invention canbe carried out in accordance with known methods, for example spreading,knife-application or pouring processes, such as curtain coating orcentrifugal moulding.

The compositions according to the invention are suitable also for thepreparation of rubber-like or thermoplastic polymers which can befurther crosslinked. For that purpose the strained cycloolefins maycontain reactive groups, for example (meth)acrylate or epoxy groups,which are covalently bonded to the cycloolefin directly or via a bridgegroup.

The compositions according to the invention can also be used asthermally curable adhesives for firm bonding to a very wide range ofmaterials, it being possible to achieve excellent peel resistance.

In addition to having high adhesive strengths, excellent processability,good surface properties (smoothness, gloss), high crosslinking densityand resistance to solvents and other liquids, the polymers according tothe invention are also distinguished in particular by very goodphysico-mechanical properties, for example high thermal stability,breaking and flexural strength and impact strength, and excellentelectrical properties, for example low conductivities, dielectricconstants and (ε)- and (tan δ)-loss factors. In addition, mention shouldbe made of the high oxygen permeability and low water absorption.Polymers composed only of carbon and hydrogen are particularly valuablefrom the ecological standpoint because they can, for example, becompletely recycled by pyrolysis or harmlessly burned.

The following Examples illustrate the invention in more detail.

USE EXAMPLES

The following catalysts are used:

[1-methyl-4-isopropylbenzene][P(C₆ H₁₁)₃ ]Ru(II)Cl₂ (catalyst A).

Cl₂ [P(C₆ H₁₁)₃ ]₂ Ru(IV)═CH--C₆ H₅ (catalyst B).

[1-methyl-4-isopropylbenzene] [P(n-butyl)₃ ] Ru(II)Cl₂ (catalyst C).

[(1-methyl-4-isopropylbenzene)RuCl₂ ]₂ (catalyst D).

Cl₂ [P(iso-C₃ H₇)₃ ]₂ Ru(IV)═CH--C₆ H₅ (catalyst E).

Cl₂ [P(cyclohexyl)₃ ]₂ Ru(IV)═CH-(4-isopropylphenyl) (catalyst F).

Cl₂ [P(cyclohexyl)₃ ]₂ Ru(IV)═CH-(4-tert-butylphenyl) (catalyst G).

Abbreviations:

DCPD: dicyclopentadiene

DSC: differential scanning calorimetry (heating rate 10° C./min)

TGA: thermogravimetric analysis (heating rate 10° C./min)

WL: weight loss of polymer powders in % in the temperature range fromroom temperature to 300° C. determined by TGA

SWE: swelling in toluene (increase in weight in % after 24 h storing intoluene)

REA: reactivity ΔH determined by DSC (in J/g)

T_(g) : glass transition temperature (° C.)

CAT: catalyst in % by weight, based on monomer, e.g. DCPD

n.d.: not determined

RT: room temperature

Examples 1-6

20 g of DCPD (technical quality, produced by Shell) are degassed for 3min under vacuum (3×10⁸ Pa) at 45° C. shortly before the catalyst isadded. The catalysts are then added and dissolved. If CH₂ Cl₂ is used assolubiliser, the mixture is subsequently degassed again under vacuum andCH₂ Cl₂ is removed. The composition is polymerised in a pill glass,curing cycle: 1 h at 80° C., 1 h at 100° C. and 2 h at 120° C.

The reactivity (ΔH) and glass transition temperature are determined byDSC. The weight loss is determined by TGA and swelling is determinedgravimetrically. The results are summarised in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Example                                                                              CAT A                                                                              CAT B                                                                              ΔH                                                                          T.sub.g                                                                           WL  SWE Remarks                                      __________________________________________________________________________    comparison                                                                           0.2  --   n.d.                                                                              <RT 15.0                                                                              n.d.                                                                              soft rubber, smell of                                                         DCPD                                         comparison                                                                           0.1  --   187 <RT n.d.                                                                              n.d.                                                                              soft rubber, smell of                                                         DCPD                                         comparison                                                                           --   0.1  288 39  19.5                                                                              94  soft solid, smell of                                                          DCPD                                         comparison                                                                           --   0.05 n.d.                                                                              <RT >30 n.d.                                                                              incompletely                                                                  polymerised                                  comparison                                                                           --   0.025                                                                              n.d.                                                                              <RT >30 n.d.                                                                              incompletely                                                                  polymerised                                  1      0.2  0.1  289 124 3.1 97  hard solid, no smell of                                                       DCPD                                         2      0.1  0.1  282 120 2.8 94  hard solid, no smell of                                                       DCPD                                         3      0.15 0.05 302 121 3.6 100 hard solid, no smell of                                                       DCPD                                         4      0.175                                                                              0.025                                                                              261 109 4.1 99  hard solid, no smell of                                                       DCPD                                         5      0.1  0.05 n.d.                                                                              123 3.7 84  hard solid, no smell of                                                       DCPD                                         6      0.05 0.05 n.d.                                                                              119 4.4 87  hard solid, no smell of                                                       DCPD                                         __________________________________________________________________________

Example 7

Example 1 is repeated, but using catalist C. The results are summarisedin Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Example                                                                              CAT C CAT B                                                                              ΔH                                                                          T.sub.g                                                                           WL  SWE Remarks                                     __________________________________________________________________________    comparison                                                                           up to 0.5                                                                           --                   no polymerisation                           comparison                                                                           --    0.1  288 39  19.5                                                                              94  soft solid                                  comparison                                                                           --    0.05 n.d.                                                                              <RT >30 n.d.                                                                              incompletely                                                                  polymerised                                 comparison                                                                           --    0.025                                                                              n.d.                                                                              <RT >30 n.d.                                                                              incompletely                                                                  polymerised                                 7      0.15  0.05 n.d.                                                                              <20 n.d.                                                                              n.d.                                                                              soft rubber, strong                                                           smell of DCPD                               __________________________________________________________________________

Examples 7 and 8

Example 1 is repeated, but using catalyst D. The results are summarisedin Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Example                                                                              CAT D CAT B                                                                              ΔH                                                                          T.sub.g                                                                           WL  SWE Remarks                                     __________________________________________________________________________    comparison                                                                           up to 0.5                                                                           --                   no polymerisation                           comparison                                                                           --    0.1  288 39  19.5                                                                              94  soft solid                                  comparison                                                                           --    0.05 n.d.                                                                              <RT >30 n.d.                                                                              incompletely                                                                  polymerised                                 comparison                                                                           --    0.025                                                                              n.d.                                                                              <RT >30 n.d.                                                                              incompletely                                                                  polymerised                                 7      0.1   0.1  286 61  11.1                                                                              n.d.                                                                              soft solid                                  8      0.15  0.05 258 28  19.5                                                                              n.d.                                                                              soft solid                                  __________________________________________________________________________

Examples 9-14

Example 1 is repeated, but using the catalyst and monomers indicated inTable 4. The results are given in Table 4.

Monomers Used ##STR17## α: tetracyclododecene (TD) ##STR18## β:cyclohexenylnorbornene (CN) (endo/exo-mixture) ##STR19## γ: DCPD

                                      TABLE 4                                     __________________________________________________________________________                 1. CAT                                                                             2. CAT                                                                             T.sub.g                                                                           WL                                                 Example                                                                              Monomer                                                                             [%]  [%]  [° C.]                                                                     [%] Observations                                   __________________________________________________________________________    comparison                                                                           α                                                                             E; 0.02                                                                            --   --  --  not polymerised                                comparison                                                                           α                                                                             F; 0.02                                                                            --   <25 --  yellow rubber                                  comparison                                                                           α                                                                             A; 0.15                                                                            --   118 18.1                                                                              polymerised                                    comparison                                                                           α                                                                             A; 0.02                                                                            --   130 11.8                                                                              polymerised                                    9      α                                                                             E; 0.02                                                                            A, 0.15                                                                            177 14.7                                                                              polymerised                                    10     α                                                                             F; 0.02                                                                            A; 0.15                                                                            174 13.3                                                                              polymerised                                    comparison                                                                           β                                                                              E; 0.02                                                                            --   <25 --  yellow rubber                                  comparison                                                                           β                                                                              F; 0.02                                                                            --   <25 --  yellow rubber                                  comparison                                                                           β                                                                              A; 0.50                                                                            --   96  --  polymerised                                    comparison                                                                           β                                                                              A; 0.15                                                                            --   79  5.9 polymerised                                    11     β                                                                              E; 0.02                                                                            A; 0.15                                                                            94  3.1 polymerised                                    12     β                                                                              F; 0.02                                                                            A; 0.15                                                                            84  4.7 polymerised                                    comparison                                                                           γ                                                                             E; 0.05                                                                            --   <25 --  yellow rubber                                  comparison                                                                           γ                                                                             F; 0.05                                                                            --   <25 --  yellow rubber                                  comparison                                                                           γ                                                                             A; 0.15                                                                            --   <25 --  yellow rubber                                  13     γ                                                                             E; 0.05                                                                            A; 0.15                                                                            60  7.8 polymerised                                    14     γ                                                                             F; 0.05                                                                            A; 0.15                                                                            73  8.0 polymerised                                    __________________________________________________________________________

Example 15

A large condenser (paper/Al foil) is predried overnight at 80° C. underhigh vacuum in a desiccator.

A mixture of 1.2 kg of degassed DCPD (technical quality, produced byShell) is mixed with 2.4 g (0.2%) of catalyst A and 1.2 g (0.1%) ofcatalyst G and this mixture is poured to the condenser in a 2 L beakerglass. The mixture is then degassed at room temperature and 0.2 mbar forabout 20 minutes and then cured in an oven: 1 hour at 50° C., 1 hour at60° C., and 1 hour at 70° C. The highly viscous formulation is thenpostcured for 15 hours at 70° C., giving a solid brown material havinggood condensing properties.

The T_(g) value determined by DSC is 33° C. The weight loss determinedby TGA is 27%.

What is claimed is:
 1. A mixture of at least one thermal carbene-freeruthenium catalyst A and at least one thermal ruthenium carbene catalystB, both of which initiate the ring-opening metathesis polymerization ofstrained cycloolefins on their own, said catalysts being present in aweight ratio of A to B from 10:1 to 1:10.
 2. A mixture according toclaim 1, wherein the ruthenium catalyst A is a compound having one ortwo ruthenium atoms.
 3. A mixture according to claim 2, wherein thecarbene-free ruthenium catalyst A is a compound of formula XI ##STR20##wherein X₀₀₁ is Cl, Br or I, and T₀₀₁ is unsubstituted or C₁ -C₆alkyl-substituted C₆ -C₁₈ arene or C₄ -C₁₇ heteroarene.
 4. A mixtureaccording to claim 1 wherein the ruthenium catalyst A contains aphosphine ligand.
 5. A mixture according to claim 4, wherein theruthenium catalyst A is a divalent-cationic compound containing at leastone phosphine ligand and a total of 2 to 5 ligands bonded to theruthenium atom and which contains acid anions for charge equalisation.6. A mixture according to claim 4, wherein the phosphine ligand conformsto formulae VII or VIIa

    PR.sub.26 R.sub.27 R.sub.28                                (VII),

    R.sub.26 R.sub.27 P--Z.sub.1 --PR.sub.26 R.sub.27          (VIIa),

wherein R₂₆, R₂₇ and R₂₈ are each independently of one another H, C₁-C₂₀ alkyl, C₁ -C₂₀ -alkoxy; C₄ -C₁₂ cycloalkyl or cycloalkoxy which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆alkoxy, or C₆ -C₁₆ aryl or C₆ -C₁₆ aryloxy which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, or C₇-C₁₆ aralkyl or C₇ -C₁₆ aralkyloxy which is unsubstituted or substitutedby C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy; R₂₆ and R₂₇ togetherare tetra- or pentamethylene or tetra- or pentamethylenedioxyl, each ofwhich is unsubstituted or substituted by C₁ -C₆ -alkyl, C₁ -C₆ haloalkylor C₁ -C₆ alkoxy, or tetra- or pentamethylene or tetra- orpentamethylenedioxyl, each of which is unsubstituted or substituted byC₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C_(C) ₆ -alkoxy and condensed with 1or 2 1,2-phenylene, or tetramethylenedioxyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy andcondensed in the 1,2- and 3,4-positions with 1,2-phenylene, and R₂₈ isas defined above; and Z₁ is linear or branched, unsubstituted or C₁ -C₄alkoxy-substituted C₂ -C₁₂ alkylene, unsubstituted or C₁ -C₄ alkyl- orC₁ -C₄ alkoxy-substituted 1,2- or 1,3-cycloalkylene of 4 to 8 carbonatoms, or unsubstituted or C₁ -C₄ alkyl- or C₁ -C₄ alkoxy-substituted1,2- or 1,3-heterocycloalkylene having 5 or 6 ring members and a heteroatom which is O or N.
 7. A mixture according to claim 1, wherein theruthenium compound A conforms to one of formulae VIII to VIIId

    R.sub.32 L.sub.1 Me.sup.2+ (Z.sup.n-).sub.2/n              (VIII),

    R.sub.32 L.sub.1 L.sub.2 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIIa),

    (R.sub.32).sub.2 L.sub.1 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIIb),

    (R.sub.32).sub.3 L.sub.1 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIIc),

    R.sub.32 (L.sub.1).sub.2 Me.sup.2+ (Z.sup.n-).sub.2/n      (VIIId),

wherein R₃₂ is a phosphine ligand of formula VII or VIIa; Me is Ru; n is1, 2 or 3; Z is the anion of an inorganic or organic acid; (a) L₁ is aligand of group A, L₁ in formula VIId being identical or different, and(b) L₂ is a ligand of group B.
 8. A mixture according to claim 1,wherein the ruthenium compound A conforms to one of formulae IX to IXd

    (R.sub.26 R.sub.27 R.sub.28 P)L.sub.1 Me.sup.2+ (Z.sub.1.sup.1-)Z.sub.2.sup.-1                            (IX),

    (R.sub.26 R.sub.27 R.sub.28 P).sub.2 L.sub.1 Me.sup.2+ (Z.sub.1.sup.1-)Z.sub.2.sup.-1                            (IXa),

    (R.sub.26 R.sub.27 R.sub.28 P)L.sub.1 L.sub.2 Me.sup.2+ (Z.sub.1.sup.-1)Z.sub.2.sup.-1                            (IXb),

    (R.sub.26 R.sub.27 R.sub.28 P).sub.3 L.sub.1 Me.sup.2+ (Z.sub.1.sup.1-)Z.sub.2.sup.1                             (IXc),

    (R.sub.26 R.sub.27 R.sub.28 P)(L.sub.1).sub.2 Me.sup.2+ ((Z.sub.1.sup.-1)Z.sub.2.sup.-1                           (IXd),

wherein Me is Ru; Z₁ and Z₂ are each independently of the other H⁻,cyclopentadienyl, Cl⁻, Br⁻, BF₄ ⁻, PF₆ ⁻, SbF6⁻, AsF₆ ⁻, CF₃ SO₃ ⁻, C₆H₅ --SO₃ ⁻, 4-methyl-C₆ H₅ --SO₃ ⁻, 3,5-dimethyl-C₆ H₅ --SO₃ ⁻,2,4,6-trimethyl-C₆ H₅ --SO₃ ⁻ or 4-CF₃ --C₆ H₅ --SO₃ ⁻ ; R₂₆, R₂₇ andR₂₈ are each independently of one another C₁ -C₆ alkyl, or cyclopentylor cyclohexyl or cyclopentyloxy or cyclohexyloxy, each of which isunsubstituted or substituted by 1 to 3 C₁ -C₄ alkyl, or phenyl or benzylor phenyloxy or benzyloxy, each of which is unsubstituted or substitutedby 1 to 3 C₁ -C₄ alkyl; L₁ is C₆ -C₁₆ arene or C₅ -C₁₆ heteroarene whichis unsubstituted or substituted by 1 to 3 C₁ -C₄ alkyl, C₁ -C₄ alkoxy,--OH, --F or Cl, or C₁ -C₆ alkyl-CN, benzonitrile or benzylnitrile, L₁in formula IXd being identical or different; and L₂ is H₂ O or C₁ -C₆alkanol.
 9. A mixture according to claim 1, wherein the rutheniumcarbene catalyst B conforms to formula X or Xa or to mixtures ofcompounds of formulae X and Xa, ##STR21## wherein Me is ruthenium;T₁ andT₂ are each independently of the other a tertiary phosphine, or T₁ andT₂ together are a ditertiary diphosphine; T₃ is H, C₁ -C₁₂ alkyl; C₃ -C₈cycloalkyl, C₃ -C₇ heterocycloalkyl having one or two hetero atomsselected from the group consisting of --O--, --S-- and --N--, C₆ -C₁₄aryl, or C₄ -C₁₅ heteroaryl having one to three hetero atoms selectedfrom the group consisting of --O--,--S-- and --N--, which areunsubstituted or substituted by C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₆ -C₁₀ aryl, C₆ -C₁₀ -aryloxy --NO₂ or halogen; T₄ is C₆-C₁₆ arene or C₄ -C₁₅ heteroarene which is unsubstituted or substitutedby 1 to 3 C₁ -C₄ -alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, --OH, F, Cl orBr, and X₀₁ and X₀₂ are each independently of the other halogen.
 10. Amixture according to claim 1, wherein the ruthenium carbene catalyst Bconforms to formulae Xb or Xc ##STR22## wherein Me is Ru, R₂₉ isα-branched C₃ -C₈ alkyl, C₅ -C₈ cycloalkyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ C₄ alkoxy, halogen or--NO₂, or C₆ -C₁₀ aryl which is unsubstituted or substituted by C₁ -C₄alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, halogen or --NO₂, T₃ is H, C₁-C₆ alkyl, C₅ -C₈ cycloalkyl which is unsubstituted or substituted by C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, halogen or --NO₂, or C₆ -C₁₀aryl which is unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, halogen or --NO₂, and T₄ is phenyl or phenylsubstituted by 1 to 3 C₁ -C₄ alkyl.
 11. A composition consisting of (a)at least one strained cycloolefin and (b) a catalytically effectiveamount of a mixture of at least one thermal carbene-free rutheniumcatalyst A and at least one thermal ruthenium carbene catalyst B, bothof which initiate the ring-opening metathesis polymerisation of strainedcycloolefins on their own, said catalysts being present in a weightratio of A to B from 10:1 to 1:10.
 12. A composition according to claim11, wherein the mixture is present in the composition in an amount from0.05 to 0.3% by weight, based on the amount of the cycloolefins present.13. A composition according to claim 11, wherein the cycloolefinconforms to formula II ##STR23## wherein Q, is a radical having at leastone carbon atom which, together with the --CH═CQ₂ -- group, forms an atleast 3-membered alicyclic ring which may contain one or more than onehetero atom selected from the group consisting of Si, P, O, N and S; andwhich is unsubstituted or substituted by halogen, ═O, --CN, --NO₂, R₁ R₂R₃ Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃(M)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀ alkyl, C₁ -C₂₀ hydroxyalkyl, C₁-C₂₀ haloalkyl, C₁ -C₆ cyanoalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇-C₁₆ aralkyl, C₃ -C₆ heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆heteroaralkyl or by R₄ --X--; or wherein two adjacent carbon atoms, whenpresent, are substituted by --CO--O--CO-- or by --CO--NR₅ --CO--; orwherein an alicyclic, aromatic or heteroaromatic ring has been fused toadjacent carbon atoms of the alicyclic ring, the former ring beingunsubstituted or substituted by halogen, --CN, --NO₂, R₆ R₇ R₈Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃(M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀hydroxyalkyl, C₁ -C₆ cyanoalkyl, C₃ C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇ C₁₆aralkyl, C₃ -C₆ heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆heteroaralkyl or by R₁₃ --X₁ --; X and X₁ are each independently of theother --O--, --S--, --CO--, --SO--, --SO₂ --, --O--C(O)--, --C(O)--O--,--C(O)--NR₅ --, --NR₁₀ --C(O)--, --SO₂ --O-- or O--SO₂ --; R₁, R₂ and R₃are each independently of one another C₁ -C₁₂ alkyl, C₁ -C₁₂perfluoroalkyl, phenyl or benzyl; R₄ and R₁₃ are each independently ofthe other C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈cycloalkyl, C₆ -C₁₆ aryl or C₇ -C₁₆ aralkyl; R₅ and R₁₀ are eachindependently of the other hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl,the alkyl groups in turn being unsubstituted or substituted by C₁ -C₁₂alkoxy or by C₃ -C₈ cycloalkyl; R₆, R₇ and R₈ are each independently ofone another C₁ -C₁₂ alkyl, C₁ -C₁₂ perfluoroalkyl, phenyl or benzyl; Mis an alkali metal and M₁ is an alkaline earth metal; and u is 0 or 1;it being possible for the alicyclic ring formed with Q₁ to containfurther non-aromatic double bonds;Q₂ is hydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀haloalkyl, C₁ -C₁₂ alkoxy, halogen, --CN or R₁₁ --X₂ --, wherein R₁₁ isC₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈cycloalkyl, C₆ -C₁₆ aryl or C₇ -C₁₆ aralkyl, and X₂ is --C(O)--O-- or--C(O)--NR₁₂ --, wherein R₁₂ is hydrogen, C₁ -C₁₂ alkyl, phenyl orbenzyl;the above-mentioned cycloalkyl, heterocycloalkyl, aryl,heteroaryl, aralkyl and heteroaralkyl groups being unsubstituted orsubstituted by C₁ -C₁₂ alkyl, C₁ -Cl₂ alkoxy, --NO₂, --CN or by halogen,and the hetero atoms of the above-mentioned heterocycloalkyl, heteroaryland heteroaralkyl groups being selected from the group consisting of--O--, --S--, --NR₉ -- and --N═; and R₉ is hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl.
 14. A process for the preparation of polymers byring-opening metathesis polymerisation, which comprises heating acomposition according to claim
 11. 15. A composition consisting of (a) asupport material and (b) a coating of a composition according to claim11, which is applied to at least one surface of a substrate selectedfrom the group consisting of glass, minerals, ceramics, plastics, wood,semi-metals, metal oxides and metal nitrides.